Radiation polymerization of olefinic monomers in the presence of metal containing catalysts

ABSTRACT

Method for the cationic polymerization of at least one olefinic monomer and more particularly the homopolymerization of a monoolefinic monomer such as isobutylene and the copolymerization thereof with a di-olefinic monomer (diene) such as butadiene and optionally another mono-olefinic monomer in the presence of, as initiator of a halide of tetravalent vanadium, titanium and zirconium, an activator and under the influence of visible ultraviolet or infra-red light.

Unite States Patent [191 Mar-elk et all.

July 29, 1975 RAlDlATION POLYMERIZATION OF OLlEFllNlC MONOMERS IN THEPRESENCE OF METAL CONTAINING CATALYSTS Inventors: Miros lav Marek; LudekToman; Jan Pecka, all of Prague, Czechoslovakia Assigneez'Ceslkoslovenska akademie ved,

Prague. Czechoslovakia Filed: July 26, 1972 Appl. No.: 275,157

Foreign Application Priority Data July 29, 1971 Czechoslovakia 5555-7]U.S. Cl 204/l59.24; 252/431 R; 252/461; 260/80.7; 260/82.l; 260/84.l;260/85.3 R; 260/87.5; 260/88.l R; 260/88.2 B; 260/9Ll A;

llnt. Cl. C08d 1/00; C08f l/l6 Fieldl oil Search... 204/l59.24;260/94.8. 94.9 B

[56] Reierences Cited UNITED STATES PATENTS 2,899,4l4 8/l959 Mertes204/l59.24

2,903,404 9/l959 Oita et al i. 2()4/l59.24 2,924.56l 2/1960Schmerling.... 204/l59.24 3,462,403 8/l969 Pendlcton 260/94.8 3,639,66l2/l972 Marek et al. 260/94.8

Primary Examiner-Paul Lieberman Assistant Examiner-Richard B. TurerAttorney, Agent, or Firm-Murray Schaffer 57 1 ABSTRACT 4 Claims, NoDrawings RADllA'llllON IPOLYMERIZATION OF OLEIFINIC MONOMERS IN THEPRESENCE OF METAL CONTAINING CATALYSTS BACKGROUND OF THE INVENTION Thisinvention relates to a method for the polymerization andcopolymerization of olefinic monomers. More particularly this inventionrelates to an improved method for the polymerization of isobutylene andits copolymerization with butadiene.

High molecular weight polyisobutylene and copolymers of isobutylene withisoprene are currently being produced at low temperatures, such as -80to 100C. The limiting factor in the low temperature method for producingbutyl rubber is the choice of an appropriate diene comonomer. Theindustrial methods now in use are all based on the copolymerization ofisobutylene with isoprene. This is the case despite the fact thatbutadiene is a cheaper and more readily available diene monomer thanisoprene. The isoprene is used rather than the butadiene because of itsmore acceptable copolymerization reactivity ratio with respect to theisobutylene. The reactivity ratio of isoprene to isobutylene isvirtually independent of temperature, while that of butadiene decreaseswith decreasing temperature. Butyl rubber having the required amount ofdouble bonds could not heretofore be prepared by the copolymerization ofisobutylene with butadiene at temperatures of about -ltlC. At highertemperatures, products having low molecular weights only were obtained,such products being entirely unsuitable for use in the production ofvulcanized articles.

There is disclosed in Czechoslovak patent application Nos. PV 2712-70and PV 2792-70, combined in U.S. Pat. application Ser. No. 133,354abandoned and refiled as Ser. No. 184,637 filed 9/28/71, that thepolymerization of monomers having olefinic double bonds in theirmolecules can becarried out using a cationic system and accelerated bylight, in the presence of halides of tetravalent titanium, vanadium andzirconium.

In accordance with the invention, it has now been found that thepolymerization carried out in the presence of the aforesaid halides andunder the influence of light (visible ultraviolet or infra red) takesplace more readily when it is conducted in the presence of certainactivators, for instance, metal oxides, hydroxides and alkoxides. Theactivators may be present in the polymerization medium in the form oftheir solutions or as fine suspensions. In the presence of theseactivators, the polymerization reaction proceeds not only more readilybut also more rapidly than heretofore possible.

SUMMARY OF THE INVENTION It is an object of this invention to provide anim' proved method for the cationic homopolymerization of olefinicmonomers.

It is another object of this invention to provide a method for thecationic copolymerization of at least one mono-olefinic monomer with adiolefinic monomer.

It is yet another object of this invention to avoid the disadvantagesassociated with the prior art methods and to provide an economically andtechnically simple and feasible method for the cationic polymerizationof at least one olefinic monomer.

Broadly speaking, the invention comprises the cationic homoandcopolymerization of two or more olefinic monomers initiated by acatalyst comprising the halides of tetravalent metals, such as vanadium,titanium and zirconium, in the presence of an activator having theformula:

M, Ay

wherein M is an alkali or alkaline earth metal, Cu, Zn, B, A], Si, Ti,Zr, V, Cr, Mo, W, U, Fe, Co, or Ni and A is an electronegative elementor O OH, OR, wherein R is alkyl or aryl, x is I or 2 and y is an integerof l to 5. Products of the reaction of hydroxy and/or alkoxy compoundsof Al or Mg with BF the aluminates, silicates, and carbonates ofunivalent and bivalent metals, activated carbon and finely dispersedmetallic Zn, Cu, Al and Fe are all also suitable for use herein. Thepolymerization is carried out at temperatures of from about 0 to 140C,using a molar ratio of catalyst to activator in the range of 10 to Thepolymerization rate may be further controlled by careful meteredintroduction of the catalyst and activator and/or by interrupting orintensifying the irradiation.

Polymerization reactions catalyzed by Friedel-Crafts halides are knownto require a so-called co-catalyst for initiating the reaction. Theco-catalyst is usually a compound of an electron donating characterwhich is able to provide the monomer or monomers with protons orcarbonium cations. The most conventional cocatalysts used are water,alcohols, ethers, carboxylic acids and the alkyl halides. However, theoxygen containing compounds of alkali metals and alkaline earth metalshave not heretofore been known to act as co-catalysts in the instanttype of reaction as in the instant invention, the application of thesecompounds is for an entirely different type of catalysis, the compoundsare indentified hereinafter as activators. Certain of the activatorsalso act as drying agents, for example KOH, and NaOH, and thepolymerization may be carried out in their presence without the thoroughpreliminary drying of the polymerization mixture. The polymerizationvelocity will depend not only upon the concentration of catalyst andintensity of the light used, but also it will depend, to a considerableextent on the concentration of activators present. When water solubleactivators are employed, the polymerization velocity is stronglyinfluenced by the molar ratio of the activator and the halide catalyst.The preferred molar ratio ranges from about 2 to 0.01. At molar ratiosof above 10, the rate of the polymerization is extremely unsatisfactory.This ratio can be varied over a broader range, if heterogeneousactivators are employed and as such will depend on the grain size of thesuspension as used, i.e., on the active surface area. The molar ratio ofthe heterogeneous activator and catalyst may then vary from 0.l to H0DETAILED DESCRIPTION As already noted, the activators utilized incarrying out the invention are compounds of the formula:

Mx Ay wherein M is an alkali or alkaline earth metal, copper, zinc,boron, aluminum, silicon, titanium, zirconium, vanadium, chromium,molybdenum, tungsten, uranium, iron, cobalt or nickel, A is anelectronegative element or O-, OI-I, or OR, wherein R is alkyl or aryl,and x and y are integers of l to 2 and l to 5 respectively. Theactivators may also be reaction products of hydroxy and/or alkoxycompounds of aluminum or magnesium with boron trifluoride, there beingincluded among the hydroxy and alkoxy compounds, the partiallyhydrolyzed aluminum and magnesium alkoxides. The latter constitute atransition between the boundary types, and namely between the hydroxidesand alkoxides of the indicated metals. There are also operable compoundsof the formulae: Al(Ol-I) X, Al(OI-l)X Al(OR) X, Al(OR)X Mg(OR)X, andMg(OI-I)X, wherein X is an electronegative element or group, such ashalogen, O,, -OI-l and the like and such as where X is OR, R being alkylor aryl. Another class of operable activators are the aluminates,silicates and carbonates of univalent and bivalent metals, activatedcarbon and finely dispersed metallic zinc, copper aluminum and iron.

In carrying out the instant process, the catalyst and activator can beadded to the reaction mixture in any order, i.e., in an arbitrary orderin increments or as a previously blended mixture. The activator having adrying effect is advantageously added as the first component to thepolymerization mixture thereby being operative to remove traces ofmoisture from the system. The polymerization velocity can be safelycontrolled by need to employ an auxiliary solvent, results in highconversions (70 to 80 the effective drying of the monomers with onecomponent of the catalyst (KOI-I, NaOI-I, etc.), and the possibility touse the more accessible and cheaper co-monomers (i.e. butadiene) therebyproviding a new and economical means for the production ofpolyisobutylene and butyl rubber.

In addition to the homopolymerization of monoolefins such as isobutyleneand the copolymerization thereof with a diolefin such as butadiene, thefollowing olefinic monomers may also be copolymerized with isobutyleneor terpolymerized with the aforesaid copolymers of isobutylene (branchedor straight chain) and butadiene: styrene, a-methylstyrene, Cl-6 alkylvinylethers, 2-chloro-butadiene-1,3, Z-methyI-butadiene- 1,3,dimethallyl, 2,3-dimethyl-butadiene-l,3, piperylene, cyclohexadiene,cyclopentadiene, alkoxybutadienes and the like.

Where desired, the solution polymerization can be carried out inaliphatic (i.e. heptane) aromatic (i.e. toluene) or halogenated (i.e.carbon tetrachloride) solvents.

The influence of light and various of the activating compounds onvanadium (IV) chloride catalyst can be seen from the following Table:

TABLE 1 influence of light and activating compounds upon vanadium (lV)chloride Catalyst Concn. of

VCL. (mol/g) VCl BaO 4.86Xl0" vcl KOH 500x10- Li tertbutoxide Monomer ofisobutylene irradiation Time (polym. Conversion MoLWt.

period) I00 60 min 60 min 45 230 000 200 W elec. lamp I00 5 min min 78130 000 30 min 62 196 000 Polymerization carried out at a temperature Ccareful metering of the catalyst and activator and by regulating theaction of the light on the reaction mixture. Overheating can be avoidedby removal of any excess heat. This method for the controlledpolymerization and copolymerization of olefinic monomers may beadvantageously and successfully carried out for the polymerization ofmonomers without the need to resort to any auxiliary solvent. Themolecular weights of the polymers and copolymers can be varied over abroad range at the given temperature by the proper combination of thecatalyst, activator and the action of light. The polymers and,especially, the high molecular weight copolymers of isobutylene withbutadiene can be obtained with an appropriate combination even atrelatively high temperatures. Butyl rubber of the required molecularweight and concentration of double bonds can be prepared by theaforesaid method at temperatures of about 40 to -30C.

Higher temperatures may also be employed and are advantageous forreasons of reaction rate etc. The polymerization which may be carriedout without the The following examples are given by way of illustrationonly and are in no-wise to be construed as limitative of the scopethereof. The examples of the polymerization reactions disclosed wereeach carried out in a glass reactor equipped with a magnetic stirrerunder anhydrous conditions in an inert atmosphere, for example ofoxygen-free argon. The application of the ultraviolet light was carriedout using a quartz apparatus. The periods of irradiation set out in theexamples represent a sum of the irradiation periods for the entirereaction, which periods were controlled so as to provide the isothermalcourse of the reaction. The molecular weights of the resultant polymerswere determined by viscometry, in n-heptane and carbon tetrachloride at20C and were calculated by means of the Flory relationship:

for n-heptane for carbon tetrachloride ried out without an auxiliarysolvent at a temperature of 40C. Vanadium (IV) chloride and lithiumtertbutoxide were used as the catalyst components in the followingamounts: 8.79Xl' mol and 2X10 mol, respectively. After introducing thecatalyst components, the reaction mixture was irradiated with a 100 Wattelectric lamp for 5 minutes. The polymerization was stopped after 30minutes by the addition of a small amount of acetone. A conversion of62% was thereby obtained. The molecular weight of the polymer was196,000.

EXAMPLE 2 EXAMPLE 3 The polymerization of 25 g of isobutylene wascarried out without an auxiliary solvent at a temperature of -40C. Afterthe catalyst components had been introduced, the reaction mixture wasirradiated for 5 minutes with a 100 Watt electric lamp. Thepolymerization was stopped after 30 minutes by the addition of ethanol.The following catalyst components were used:

a. Vanadium (IV) chloride (8.79 l0' mol) and potassium hydroxide (1 10mol) which potassium hydroxide was introduced in the form of a finesuspension in n-heptane. The conversion was 72% and the molecular weightof the polymer was 137,640.

b. Vanadium (IV) chloride (8.79Xl0' mol) and sodium hydroxide (2 10'mol), the latter being introduced as a fine suspension in n-heptane. Theconversion was 72% and the molecular weight of the polymer was 140,000.

EXAMPLE 4 The polymerization of 25 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of 40C. Titanium (IV)chloride (1.42 l0 mol) and sodium hydroxide (2.2 mol) were used ascocatalysts. The sodium hydroxide was introduced as a fine suspension inn-heptane. After the catalyst components had been introduced, thereaction mixture was irradiated with a 200 Watt electric lamp for 2minutes. The polymerization was terminated after 30 minutes by theaddition of ethanol. The conversion amounted to 50% and the polymer hada molecular weight of 130,000.

EXAMPLE 5 The polymerization of 25 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of 40C. Titanium (IV)chloride (1.42 l0" mol) and aluminium oxide (3.2)(10 mol) were used ascocatalyst. The aluminium oxide was introduced as a fine suspension inn-heptane. The reaction mixture was irradiated for 5 minutes with a 100Watt electric lamp following introduction of the catalyst components.The

polymerization was stopped after 30 minutes by the addition of ethanol.There was realized a conversion of 65%. The polymer had a molecularweight of 144,000.

EXAMPLE 6 The polymerization of 24 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of -40C. Titanium (IV)chloride 1.42X10 mol) and vanadium (IV) oxide (l.2 l0' mol) as a finesuspension in heptane were used as the co-catalyst components. After thetwo components had been introduced, the reaction mixture was irradiatedfor 1 hour with a 60 Watt electric lamp. The polymerization was stoppedby addition of ethanol. The conversion amounted to 10.4% and the polymerhad a molecular weight of 255,500.

EXAMPLE 7 The polymerization of 25 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of 40C. Titanium (IV)bromide (1.5Xl0 mol) and magnesium oxide (2.4)(10' mol) were used ascocatalyst components. Magnesium oxide was introduced in the form of itssuspension in heptane. After introduction of the two catalystcomponents, the reaction mixture was irradiated for 5 minutes with a 500Watt electric lamp. The polymerization was interrupted after 20 minutesby the addition of ethanol. The conversion amounted to 51.3% and themolecular weight of the polymer was 150,000.

EXAMPLE 8 The polymerization of 25 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of -l00C. Titanium (IV)iodide (1.5 l0' mol) and calcium oxide (l.l l0 mol) were used asco-catalyst components. The calcium oxide was introduced as itssuspension in heptane. After the two catalyst components had beenintroduced, the reaction mixture was irradiated with a 200 Watt electriclamp for 10 minutes. The polymerization was stopped at 120 minutes bythe addition of ethanol. The conversion amounted to 6% and the polymerhad a molecular weight of 1,550,000.

EXAMPLE 9 The polymerization of isobutylene was carried out in heptane(concentration 50% (w/w)) at a temperature of -50C. Vanadium (IV)chloride (l.8 104 mol) and ferric oxide (l.1 10- mol) were used ascocatalyst components. The ferric oxide was introduced in the form of aheptane suspension. After introducing the two catalyst components into30 g of the heptane solution containing the isobutylene, the reactionmixture was irradiated with a 200 Watt mercury discharge lamp for 35minutes. The polymerization was stopped after 30 minutes by the additionof ethanol. The conversion amounted to and the polymer had a molecularweight 250,000.

EXAMPLE 10 The polymerization of isobutylene was carried out in atoluene solution (concentration 50% (w/w)) at a temperature of -60C.Vanadium (IV) chloride (l.5 10" mol) and calcium hydroxide (1.8Xl0' mol)were used as co-catalyst components. The calcium hydroxide wasintroduced as a suspension in heptane. After introducing the twocatalsyt components into 30 g of isobutylene solution, the reactionmixture was irradiated for 10 minutes with a 200 Watt electric lamp. Thepolymerization was terminated by the addition of ethanol at a conversionof 69% and a molecular weight of the polymer of 145,000.

EXAMPLE 1 l The polymerization of isobutylene was carried out without asolvent at a temperataure of 30C. VCI (3 10 mol) and a heptanesuspension of M;, (2.5 l0 mol) were added to 23 g of isobutylene. Thereaction mixture was irradiated with a 500 Watt electric lamp for 2minutes. The polymerization was stopped after 30 minutes. 15 g of thepolymer were obtained having a molecular weight 175,000.

EXAMPLE l2 VCl (5 10' mol) and 3X10 mol of CuO, in a heptane suspensionwere added to 20 g of isobutylene at 25C. After irradiation with a 500Watt electric lamp for 2 minutes polyisobutylene was obtained having amolecular weight 100,000 at a conversion of 40%.

EXAMPLE 13 The copolymerization of 20 g of isobutylene with 4 g ofbutadiene was carried out at a temperature of 40C. VCL, (6 1O mol) andM00 (2.5X10' mol) were added to the mixture of monomers which was thenirradiated with a 500 Watt electric lamp for 5 minutes. Thecopolymerization was stopped after 30 minutes by the addition ofethanol. The conversion amounted to 30% and the molecular weight of thecopolymer was 325,000.

EXAMPLE 14 The copolymerization of isobutylene and butadiene was carriedout at a temperature of 40C. VCL, (8X10' mol) and a KOl-l suspension inheptane (5Xl0 3 mol) were added to 25 g of the mixture of monomers whichcontained 20% w/w of butadiene. The reaction mixture was irradiated witha 500 Watt electric lamp for 1 minute and the polymerization stoppedafter 45 minutes. The conversion amounted to 55%. The copolymercontained 70% of insoluble gels.

EXAMPLE 15 The copolymerization of g of isobutylene and 1 g of isoprenewas carried out in accordance with the disclosure of EXAMPLE 14. Thecopolymer formed had a molecular weight of 105,000 at a conversion of30%.

EXAMPLE 16 The polymerization of isobutylene was carried out without anauxiliary solvent. Into g of isobutylene there were introduced:

a. Vanadium (IV) chloride (8.79Xl0 mol) and aluminum sec-butoxide (6X 10 mol). The polymerization was carried out at a temperature of 40C andby means of irradiation with a 100 Watt electric lamp for 5 minutes. Thepolymerization was stopped after 25 minutes by the addition of ethanolat a conversion of 70% and a molecular weight of 220,000.

b. Vanadium (IV) chloride (5.86 10' mol) and 8X10 mol of aluminumsec-butoxide saturated with boron trifluoride. The polymerization wascarried out at a temperature of 40C by means of irradiation with a Wattelectric lamp for 5 minutes. The polymerization was stopped after 20minutes by the addition of ethanol at a conversion of 69% and amolecular weight of 250,000.

EXAMPLE 1 7 The terpolymerization of 30 of isobutylene, 4.4 g ofbutadiene and l g of styrene was carried out at a temperature of 40C.Vanadium (IV) chloride (9.8X10 mol) and a heptane suspension of sodiumethoxide (5.1 10 mol) were added to the mixture of monomers. The sodiumethoxide was prepared by the reaction of ethanol and metallic sodium,followed by heating to 200C in vacuo for 2 hours and a final heating atthis temperature in a stream of hydrogen for 1 hour. After the catalystcomponents had been introduced, the reaction mixture was irradiated witha 100 Watt electric lamp for 5 minutes. The reaction was stopped after60 minutes by the addition of 10 cc. of ethanol at a conversion of 52%.The molecular weight of the product was 152,000 and the concentration ofthe double bonds l.72%.

EXAMPLE 18 The copolymerization of 22 g of isobutylene and 1.5 g of2,3-dimethylbutadiene-1,3, was carried out without an auxiliary solvent.Vanadium (IV) chloride (8.79 l0 mol) and potassium phenoxide (6X10 mol),as a suspension in heptane, were introduced into the mixture ofmonomers. The reaction mixture was then irradiated with a 100 Wattmercury discharged lamp for 10 minutes and the reaction was stoppedafter 60 minutes by the addition of 10 cc. of ethanol. The resultingcopolymer had a molecular weight of 210,000 and contained 0.95% ofdouble bonds at a conversion of 50.8%.

EXAMPLE 19 The copolymerization of 25 g of isobutylene and 2.2 g ofchloroprene was carried out without an auxiliary solvent at atemperature of -40C. Vanadium (IV) chloride (1 10 mol) and lithiumtertbutoxide (5 l0 6 mol) were introduced into the mixture of monomers.Ther reaction mixture was then irradiated with a 100 Watt electric lampfor 5 minutes. The reaction was stopped after 60 minutes by the additionof 10 cc. of ethanol at a conversion of 49%. The polymer had a molecularweight of 170,000. The product contained 1.17% of chlorine.

EXAMPLE 20 The copolymerization of isobutylvinylether with isobutylenewas carried out at a temperature of 50C. Vanadium (IV) chloride (1Xl0mol) and barium hydroxide (5 10' mol) were added to the monomer mixturewhich consisted of 30 g of isobutylene and 2 g of isobutylvinylether.The reaction mixture was then irradiated with a 100 Watt electric lampfor 5 minutes. The reaction was stopped by the addition of 10 cc. ofethanol after 50 minutes. The conversion amounted to 38% and theintrinsic viscosity of the product amounted to 1.3 (heptane, 20C).

EXAMPLE 21 The polymerization of a 10% solution of isobutylene in hexanewas carried out at a temperature of 30C at continuous stirring. Thecatalyst was used as a 0.5%

suspension in hexane and was prepared by saturation of a 10% suspensionof aluminum hydroxide in hexane with boron trifluoride at 10C. The free3E was removed by distillation of about a half of the hexane, andaddition of 0.5 mol of TiCL, per mole of the aluminum compound. Thealuminum hydroxide used was obtained by precipitation of aluminumsulfate with ammonia or alkaline aluminate with carbon dioxide in anaqueous medium, centrifuged, washed with water and dehydrated by butanoland hexane. By saturation of the hydroxide with BF a green complex wasformed which turned yellow after the addition of TiCL, thereto. Afterthe catalyst had been added, the reaction mixture was irradiated with a200 Watt electric lamp for 30 minutes. The polymerization was stopped bythe addition of acetone after 30 minutes at a conversion of 99% andmolecular weight of 700,000.

EXAMPLE 22 The polymerization of a 10% solution of isobutylene in hexanewas carred out at C with continuous stirring of the solution and bymeans of 0.5% of a catalyst suspension in hexane. The catalyst wasprepared from a solution of a partially hydrolyzed aluminum secbutoxidein hexane, which was saturated with boron trifluoride at. 10C. Afterhalf of the volume of hexane was distilled off and 0.5 mol of TiC1 per 1mole of aluminum alkoxide was added, the original green color of thesuspension turned yellow. The suspension obtained was used as acatalyst. The hydrolysis of an about 10% solution of aluminum secbutoxide in sec butanol was carried out at 50C using a calculated amountof water 1 mol of water per 2 mol of alkoxide) which was added as asolution in alcohol under continuous stirring within a period of 1 hour.After the hydrolysis, the alcohol was distilled off from the reactionmixture in vacuo and the product thusly obtained dissolved in hexane andsaturated with BF After introduction of the catalyst, the polymerizationmixture was irradiated with a 200 Watt electric lamp for 30 minutes. Thereaction was stopped after 1 hour by the addition of acetone at aconversion of 98% and a molecular weight of 180,000.

EXAMPLE 23 The polymerization of a 10% solution of isobutylene in hexanewas carried out at 0C under continuous stirring and with 0.5% of acatalyst suspended in hexane. The catalyst was prepared fromdihydroxyfluoroaluminum which was washed with water, dehydrated withabsolute alcohol and hexane, suspended in hexane and saturated with B1at 10C. The suspension was used after the addition of 0.5 mol of TiClper mol of the aluminum compound. After addition of the catalyst, thereaction mixture was irradiated with a 200 Watt electric lamp for 30minutes. The polymerization was stopped after 1 hour by the addition ofacetone at a conversion of 58% and a molecular Weight of 150,000.

EXAMPLE 24 The polymerization of isobutylene was carried out with thecatalyst prepared as described in EXAMPLE 21. Magnesium hydroxide wasused in place of the aluminum hydroxide, which was obtained frommagnesium sulfate or another magnesium salt by precipitation with sodiumhydroxide in an aqueous medium and then treated similarly as thealuminum hydroxide in EXAM- PLE 21. After the catalyst had beenintroduced into the polymerization mixture, it was irradiated with a 200Watt electric lamp under continuous stirring for 30 minutes. Thepolymerization was stopped by the addition of acetone after 1 hour at aconversion of 97% and a molecular weight of 160,000.

EXAMPLE 25 The polymerization of a 10% (w/w) solution ofisobutylene inhexane was carried out at 0C under continuous stirring with 0.5% (w/w)of the catalyst which was suspended in hexane. The catalyst was preparedby saturation of dipropoxychloroaluminum with 31 in a hexane solution.The free 8E was removed by distilling off half of the hexane. Vanadium(IV) chloride was added in a molar ratio to the aluminum in thealkoxychloroaluminum equal to 0.5. After the catalyst had beenintroduced, the polymerization mixture was irradiated with a 200 Wattelectric lamp for 30 minutes. The reaction was stopped after 1 hour bythe addition of acetone at a conversion of and a molecular weight of120,000.

EXAMPLE 26 The terpolymerization of 25 g of isobutylene, 4.4 g ofbutadiene and 1.2 g of styrene was carried out at 60C without anauxiliary solvent. Vanadium (IV) chloride (8X10 mol) and 0.01 g of anactivator in the form of a hexane suspension were used as theco-catalyst components. The activator was prepared by introducing BF},into a 10% solution of aluminum tertbutoxide in hexane at a temperatureof 10C to maximal saturation. The greenish, voluminous precipitatethereby obtained was treated with 1 mol TiBr, per 1 mol of alkoxide andthe resulting suspension used a activator. After introclucing thevanadium (1V) chloride and the activator into the monomer mixture, itwas irradiated with a 200 Watt electric lamp for 4 minutes. The reactionwas stopped after 30 minutes by the addition of ethanol at a conversionof 59% and a molecular weight of 210,000. The terpolymer contained 1.4%of double bonds.

EXAMPLE 27 The terpolymerization of 25 g of isobutylene, 0.3 g ofisoprene and 3 g of butadiene was carried out without an auxiliarysolvent at 40C. Vanadium (IV) chloride (1X10 mol) and 0.01 g of a hexanesuspension of an activator were introduced into the reaction mixture.The activator was prepared by mixing chloroethane solutions of aluminumsec butoxide and AlCl in a molar ratio of 1:3. The mixture was thendiluted with dry hexane, the precipitate formed decanted with dryhexane, treated with Til in a molar ratio of 1:1 to aluminum secbutoxide and then used as its suspension. After the catalyst andactivator had been introduced, the reaction mixture was irradiated witha 200 Watt electric lamp for 5 minutes. The reaction was stopped by theaddition of ethanol at a conversion of 69% and a molecular weight of290,000. The terpolymer thus obtained contained 2.1% of double bonds.

EXAMPLE 28 The polymerization of 30 g of a C -fraction was carried outat a temperature of 78C. The C -fraction was previously twice washedwith 5% sulfuric acid and dried over potassium hydroxide and consistedof: 1,3- butadiene 730 ppm, isobutylene 45.4% (w/w), butene- 1 20.1%w/w, trans-butene-Z 13.2% w/w. cisbutene-2 8.8% w/w, isobutane 1.8% w/wand n-butane 10.6% w-w. Vanadium (IV) chloride (1.5X10 mol) and 0.01 gof the activator were used as the catalyst cocomponents. The activatorwas prepared by the addition of resublimed AMI] in a 10% hexane solutionof aluminum sec butoxide in a molar ratio of 3: 1. The suspension wasthoroughly blended in a ball mill and then employed. After introducingthe catalyst and activator, the C -fraction ws irradiated with a 200Watt electric lamp for 5 minutes. The reaction was terminated after 60minutes by the addition of ethanol at a conversion of 98% (based onisobutylene) and a molecular weight of 210,000.

EXAMPLE 29 The polymerization of 30 g of isobutylene was carried outwithout an auxiliary solvent at -50C. The following catalyst componentswere used:

a. Vanadium (IV) bromide (l l mol) and aluminum hydroxide in a heptanesuspension (prepared as described in EXAMPLE 21, 6X10 mol). Afterintroducing the catalyst components, the reaction mixture was irradiatedwith a 200 Watt electric lamp for 3 minutes. The reaction was terminatedafter 30 minutes by the addition of ethanol at a conversion of 76% and amolecular weight of 250,000.

b. Vanadium (IV) iodide (1.5Xl0 mol) and magnesium hydroxide (preparedas in EXAMPLE 24) in a heptane suspension (5 l0 mol). After introducingthe catalyst and activator, the reaction mixture was irradiated with a200 Watt electric lamp for 2 minutes. The reaction was stopped after 30minutes by the addition of ethanol at a conversion of 72% and amolecular weight of 279,000.

EXAMPLE 30 The polymerization of 25 g of isobutylene was carried outwithout an auxiliary solvent at 40C in the presence as catalyst ofvanadium (IV) chloride. The VCl, (9X10 mol) was added to the isobutyleneunder continuous stirring and, after addition of an activator, thereaction mixture was irradiated with a 200 Watt electric lamp for 2minutes. The reaction was terminated after minutes by the addition ofethanol. The following activators were used:

a. 0.8 g of powdered copper in heptane suspension;

b. 0.5 g of powdered pyrophoric iron in heptane suspension;

c. 0.55 g of powdered zinc in heptane suspension;

(1. 0.25 g of powdered aluminum in heptane suspension.

A rubber-like polymer was formed in all of the cases having a molecularweight of about 180,000. The conversion amounted to about 70%.

EXAMPLE 31 The polymerization of 30 g of isobutylene was carried outwithout an auxiliary solvent and with vanadium (IV) chloride as thecatalyst at -50C. The VCL, (5.8)(10 mol) was added to the isobutyleneunder continuous stirring. Following the addition of an activator, thereaction mixture was irradiated with a 200 Watt electric lamp for 3minutes. The reaction was stopped after 30 minutes by the addition ofethanol. The following activators were used:

a. 0.25 g of magnesium aluminate in heptane suspension;

b. 0.30 g of magnesium silicate in heptane solution.

c. 0.20 g of amorphous powdered silicon dioxide in heptane suspension. Arubber like polymer having a molecular weight of about 290,000 wasobtained in all cases at a conversion of 79%.

EXAMPLE 32 The polymerization of 26 g of isobutylene was carried outwithout an auxiliary solvent at 40C. Vanadium (IV) chloride (8.9 10 mol)was used as the catalyst and n-butyl orthoborate (6 10 mol) as theactivator. After both of the components had been introduced, thereaction mixture was irradiated with a 200 Watt electric lamp for 2minutes. The polymerization was terminated after 30 minutes by theaddition of ethanol at a conversion of 78% and a molecular weight of thepolymer of 280,000.

EXAMPLE 33 The polymerization of 27 g of isobutylene was carried outwithout an auxiliary solvent at a temperature of -30C. Active carbon(0.1 g) and 7.2X10 mol of vanadium (IV) chloride were added into thecontinuously agitated isobutylene in a stream of nitrogen. The reactionmixture was irradiated with a 200 Watt electric lamp for 2 minutes andthe reaction stopped by the addition of ethanol at a conversion of 65%and a molecular weight of 150,000.

EXAMPLE 34 The copolymerization of isobutylvinylether with2,3-dimethylbutadiene-l ,3 was carried out without an auxiliary solventat a temperature of 40C. 2,3-dimethylbutadiene-1,3 (5g) was added to 25g of isobutylvinylether, the mixture then cooled to the polymerizationtemperature and 1.1X10 mol of titanium (IV) iodide and 3.2 10 mol ofaluminum oxide in heptane suspension were introduced. The reactionmixture was irradiated with a 200 Watt electric infrared lamp for 2minutes. The polymerization was stopped by the addition of ethanol after30 minutes at a conversion of 5.8% and an intrinsic viscosity of thecopolymer of 1.43 (CCl 20C).

EXAMPLE 35 isobutylene (25 g) was polymerized without an auxiliarysolvent at -50C using 5X10 mol of vanadium (IV) chloride. After anactivator had been added, the reaction mixture was irradiated with a 200Watt electric lamp for 3 minutes and after 30 minutes, the reaction wasstopped by the addition of ethanol at a conversion of 74%. The followingcompounds were used as activators:

a. 0.28 g of potassium carbonate in heptane suspenb. 0.30 g of magnesiumcarbonate in heptane suspension:

c. 0.25 g of ferrous carbonate in heptane solution; d. 0.26 g of zinccarbonate in heptane suspension. A rubber-like polymer was formed in allof the cases, which was of a similar character and properties to thatobtained in EXAMPLE 31.

What is claimed:

1. A method for the polymerization of isobutylene, which comprisessubjecting to a source of light selected from the group consisting ofultraviolet light, visible light, and infrared light at a temperaturebetween about C. and about -l40C. an isobutylene feed selected from thegroup consisting of (a) essentially isobutylene and (b) essentially amixture of isobutylene and butadiene in the presence of at least onehalide catalyst selected from the group consisting of tetravalentvanadium, titanium and zirconium halides and in the presence of at leastone activator for said halide catalyst selected from the groupconsisting of (i) an oxide, a hydroxide, an alltoxide, and an aryloxideof a metal selected from the group consisting of (ii) the alkali metalsand the alkaline earth metals, the molar ratio of said halide catalystto said activator ranging from to 10 part of halide catalyst to 1 partof activator.

2. A method according to claim 1, in which the polymerizable mixtureconsists essentially of isobutylene.

3. A method according to claim 1, in which the polymerizable mixtureconsists essentially of isobutylene and butadiene.

4. A method for the polymerization of isobutylene and mixtures ofisobutylene and butadiene, which comprises subjecting isobutylene ormixtures of isobutylene and butadiene to a source of light selected fromthe group consisting of ultraviolet light, visible light, and infraredlight at a temperature between about 0C. and about -l40C. in thepresence of vanadium tetrachloride and in the presence of barium oxide.the molar ratio of said vanadium tetrachloride to said barium oxideranging from 10 to 10' part of vanadium tetrachloride to 1 part ofbarium oxide. l l l

1. A METHOD FOR THE POLYMERIZATION OF ISOBUTYLENE, WHICH COMPRISESSUBJECTING TO A SOURCE OF LIGHT SELECTED FROM THE GROUP CONSISTING OFULTRAVIOLET LIGHT, VISIBLE LIGHT, AND INFRARE LIGHT AT A TEMPERATUREBETWEEN ABOUT 0*C AND ABOUT -140*C AN ISOBUTYLENE FEED SELECTED FROM THEGROUP CONSISTING OF (A) ESSENTIALLY ISOBUTYLENE AND (B) ESSENTIALLY AMIXTURE OF ISOBUTYLENE AND BUTADIENE IN THE PRESENCE OF AT LEAST ONEHALIDE CATALYST SELECTED FROM THE GROUP CONSISTING OF TETRAVALENTVANADIUM, TITANIUM AND ZIRCONIUM HALIDESAND IN THE PRESENCE OF AT LEASTONE ACTIVATOR FOR SAID HALIDE CATALYST SELECTED FROM THE GROUPCONSISTING OF (I) AN OXIDE, A HYDROXIDE, AN ALKOXIDE, AND AN ARYLOXIDEOF A METAL SELECTED FROM THE GROUP CONSISTING OF (II) THE ALKALI METALSANDTHE ALKALINE EARTH METALS, THE MOLAR RATIO OF SAID HALIDE CATALYST TOSAID ACTIVATOR RANGING FROM 10-3 PART OF HALIDE CATALYST TO 1 PART OFACTIVATOR.
 2. A method according to claim 1, in which the polymerizablemixture consists essentially of isobutylene.
 3. A method according toclaim 1, in which the polymerizable mixture consists essentially ofisobutylene and butadiene.
 4. A method for the polymerization ofisobutylene and mixtures of isobutylene and butadiene, which comprisessubjecting isobutylene or mixtures of isobutylene and butadiene to asource of light selected from the group consisting of ultraviolet light,visible light, and infrared light at a temperature between about 0*C.and about -140*C. in the presence of vanadium tetrachloride and in thepresence of barium oxide, the molar ratio of said vanadium tetrachlorideto said barium oxide ranging from 103 to 10 3 part of vanadiumtetrachloride to 1 part of barium oxide.